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Electrochemical reduction of carbon dioxide on lead and copper electrodes

Nastase Raluca Ngassimou Abba

End products
1. Hydrocarbons: Methane Propane Ethylene 2. Oxygenated molecules: Methanol Ethanol Formic acid Oxalic acid

Parameters
- applied potential - buffer strength - local pH - local CO2 concentration - CO2 pressure - surface crystal structure of the electrodes

Electrochemical reduction of CO2 at Cu


2H+ + 2e- H2 E0=0.0V vs SHE 2CO2 +12H+ +12e- C2H4 + 4H2O E0= 0.079V vs SHE CO2 + 8H+ +8e-CH4 + 2H2O E0= 0.169V vs SHE CO2 + 2H+ +2e-CO + H2O E0= -0.103V vs SHE CO2 + H+ +2e-HCOO- E0= -0.225V vs SHE

Fig. 1. Voltammograms obtained in phosphate solutions with Ar: (a), CO (b), and CO2 (c) at pH 6.8, and with 0.1MKHCO3 saturated with CO2 (d) at pH 6.8.

Fig. 2. Partial current data. (Conditions: 0.1M KHCO3, 19C, CO2 bubbled, bulk [H+] = 1.55 107 M, bulk [CO2] = 3.41 102 M. Estimated local [H+] and [CO2] values for polarisation measurements

The CO2 reaction step

Reaction pathways
Fig. 3. The main reaction pathways at the electrode surface, with adsorbed CO blocking the majority of the surface and hydrocarbon products being formed by the further reduction of adsorbed CO.

Current efficiencies at different potentials


Fig. 4. Current efficiencies at different potentials (0.1M KHCO3, CO2 bubbled).

Electrochemical reduction of CO2 at Pb


Three electrode conventional cell Voltammetric experiments were carried out in an onecompartment conventional three electrode Pyrex cell (V=15 cm3) Working electrode : a lead wire with a geometric surface area of 0.42cm2 Counter electrode: vitreous carbon plate Reference electrodes: Hg/Hg2Cl2/KCl sat. (aqueous medium) and Ag/AgCl (propylene carbonate) Electrochemical measurements : PC controlled AutoLab PGSTAT 302 Electrochemical Interface

Electrochemical reduction of CO2 at Pb


Three electrode spectroelectrochemical cell Designed with a CaF2 IR transparent window Working electrode : a Pb disc of 8 mm diameter. Counter electrode: vitreous carbon plate Reference electrode: Hg/Hg2Cl2/KCl sat. (aqueous medium) Ag/AgCl (propylene carbonate) Fourier transform infrared spectrometer Bruker IFS 66v/S. OPUS 5.5 software. Methods: SPAIRS and chronoamperometry. Spectra: DA = DR/R0 = (RE2 RE1)/RE1

Results and discussion


Aqueous medium Fig.5. Voltammograms of a Pb electrode in 0.1 MNaOH recorded at 1 mV s1. (a) In supporting electrolyte. (b) After bubbling CO2 until pH = 8.6.
Propylene carbonate Fig.6. Voltammograms of a Pb electrode in 0.2M TEAPPrC recorded at 50mVs1 and 25 C in the absence (a) and the presence of a CO2 -saturated solution (b).

Spectroscopic study in aqueous medium


Fig. 7 FTIR spectra in spectroelectrochemical cell without applied potential to a Pb electrode during CO2 bubbling in 0.5 M NaOH; DR/R = (Rti Rt=0)/Rt=0, the reference spectrum, Rt=0, was recorded at t = 0. (a) CO2 between 5 and 30 s. (b) CO2 between 40 and 90 s. (c) CO2 between 100 and 200 s.

Fig. 8. Transmission spectra of KHCO3 (a) and K2CO3 (b) diluted in KBr pellets.

Fig.9. SPAIR spectra on a Pb electrode after bubbling CO2 in 0.1 MNaOH until pH = 8.6;DR/R = (RE2 RE1)/RE1, where the reference spectrum, RE1,was taken at E = 1.8 V vs.SCE. (a) Electrode potential from 1.0 V to 1.45 V vs. SCE. (b) Electrode potential from 1.5 V to 1.8 V vs. SCE.

Reaction step

Spectroscopic study in propylene carbonate


Fig. 10. Reference spectra of 0.2M TEAPPrC recorded at 2.8V vs. Ag/AgCl (a), CO2
(b), formate (c) and oxalate (d) recorded in 0.2M TEAPPrC.

Reaction step

Conclusions
Propylene carbonate: Better characterization Mass transfer process Main reaction product: oxalate Aqueous medium: Predominant species: hydrogen carbonate ions CO2 : not absorbed at cathodic electrode potential Exclusive organic species : formate Copper electrode: Multiple reaction pathways Main product: CO

References
A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper- M. Gatrell, N. Gupta : Journal of Electroanalytical Chemistry 594 (2006) FTIR spectroscopy study of the reduction of carbon dioxide on lead electrode in aqueous medium- B. Innocent, D. Pasquier, F. Ropital, F. Hahn, J.-M. Leger, K.B. Kokoh: Applied Catalysis B: Environmental 94 (2010) 219224 Electroreduction of carbon dioxide at a lead electrode in propylene carbonate: A spectroscopic study- B. EneauInnocent, D. Pasquier, F. Ropital, J.-M. Lger, K.B. Kokoh: Applied Catalysis B: Environmental 98 (2010) 6571

Thank you!

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